Chapter 7: Diffusion

ISSUES TO ADDRESS...
• How does diffusion occur?

• Why is it an important part of processing?

• How can the rate of diffusion be predicted for

some simple cases?

• How does diffusion depend on structure

and temperature?

Chapter 5 - 1
Diffusion
Diffusion - Mass transport by atomic motion
Mechanisms
• Gases & Liquids – random (Brownian) motion

• Solids – vacancy diffusion or interstitial diffusion

Chapter 5 - 2
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Diffusion
• Interdiffusion: In an alloy, atoms tend to migrate from regions of high
conc. to regions of low conc.
Initially After some time

Figs. 5.1 & 5.2,

Callister &
Rethwisch 9e.

Interatomic diffusion
Chapter 5 - 3
 Diffusion
• Self-diffusion: In an elemental solid, atoms also migrate.

Label some atoms

After some time
C
C
A D
A
D
B
B

Chapter 5 - 4
Diffusion Mechanisms
Vacancy Direct Exchange Indirect Exchange (self-)

Direct Interstitial Kick-out Frank-Turnbull

Chapter 5 - 5
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 Diffusion Mechanisms
Vacancy Diffusion:
• atoms exchange with vacancies
• applies to substitutional impurities atoms
• rate depends on:
-- number of vacancies
-- jumping characteristics of an atom in the lattice.

increasing elapsed time

Chapter 5 - 6
Diffusion Mechanisms
• Interstitial diffusion – smaller atoms can
diffuse between atoms.

More rapid than vacancy diffusion

Fig. 5.3 (b), Callister & Rethwisch 9e.
rate depends on:
-- number of interstitial sites
-- jumping characteristics of an atom in the lattice. Chapter 5 - 7
Interstitial Sites
Octahedral Sites Tetrahedral Sites

FCC: 8
FCC:
=12/4 +1
=4

BCC
BCC:
= (6*4)/2
=12/4 +6/2
=12
=6

Chapter 5 - 8
Interstitial Sites
Octahedral Sites Tetrahedral Sites

FCC: 8
FCC:
=12/4 +1
=4

BCC
BCC:
= (6*4)/2
=12/4 +6/2
=12
=6

Chapter 5 - 9
 Processing Using Diffusion
• Case Hardening:
Chapter-opening photograph, Chapter 5,
Callister & Rethwisch 9e. (Courtesy of
Surface Division, Midland-Ross.)
-- Diffuse carbon atoms
into the host iron atoms
at the surface.
-- Example of interstitial
diffusion is a case
hardened gear. https://doitpoms.admin.cam.ac.uk/miclib/micrograph.php?id=281
Carburization
Quenching /
Original Part Carburizing Tempering Carburized Part

4
Features a hardened
The carbon content of Formation of surface or case
Typically a low-carbon
the surface is martensite.
steel. .
increased. Relieving surface
stresses. Chapter 5 - 10
Adapted from Dr. Simge Cinar’s Lecture Notes, METE230, METU, Ankara,Turkey
 Processing Using Diffusion
• Doping silicon with phosphorus for n-type semiconductors:
• Process: 0.5 mm
1. Deposit P rich
layers on surface.
magnified image of a computer chip

silicon
2. Heat it.
3. Result: Doped light regions: Si atoms
semiconductor
regions.

light regions: Al atoms

silicon
Adapted from Figure 18.27, Callister &
Rethwisch 9e.
Chapter 5 - 11
Diffusion
• How do we quantify the amount or rate of diffusion?

flux :the rate at which atoms cross a unit area. (gram or

atoms)/cm2 -sec

• Measured empirically
– Make thin film (membrane) of known cross-sectional area
– Impose concentration gradient
– Measure how fast atoms or molecules diffuse through the
membrane

M=
mass J  slope
diffused
time
Chapter 5 - 12
 Diffusion
A mass balance upon a differential volume
element perpendicular to the mass flow direction.
dZ
• Mass in - mass out = Accumulation
By considering some time interval dt Jin Jout A

• Rate in - rate out = Rate accumulation

where 
 ( A  dZ )  C
= A  dZ
 
C
• Rate accum. =
t t C

• Rate mass in= (JA)1

Since dZ is a differential length
Z
J in
• Rate mass out = (JA)1 + ( JA ) dZ dJ
Z J out
dZ

Z
J C
Continuity Equation − =
Z t
Chapter 5 - 13
Adapted from Prof. Dr. Sakir Bor’s Lecture Notes, METE403, METU, Ankara,Turkey
Steady-State Diffusion
J C
Rate of diffusion independent of time − = constant
Z t

Flux proportional to concentration gradient =

C1 C 1
Fick’s first law of diffusion

C2 C2

x1 x x2
x1
x2
J D  diffusion coefficient

x Chapter 5 - 14
Example: Chemical Protective
Clothing (CPC)
• Methylene chloride is a common ingredient of paint
removers. Besides being an irritant, it also may be
absorbed through skin. When using this paint
remover, protective gloves should be worn.
• If butyl rubber gloves (0.04 cm thick) are used, what
is the diffusive flux of methylene chloride through the
glove?
• Data:
– diffusion coefficient in butyl rubber:
D = 110 x10-8 cm2/s
– surface concentrations: C1 = 0.44 g/cm3
C2 = 0.02 g/cm3

Chapter 5 - 15
Example (cont).

• Solution – assuming linear conc. gradient

glove
C1 2
tb =
6D
paint skin
remover
C2 Data: D = 110 x 10-8 cm2/s
x1 x 2 C1 = 0.44 g/cm3
C2 = 0.02 g/cm3
x2 – x1 = 0.04 cm

Chapter 5 - 16
Non-steady State Diffusion
• The concentration of diffusing species is a function of
both time and position C = C(x,t)
• In this case Fick’s Second Law is used dZ

J C   C   C i
− =  Di  = Jin Jout A

Z t Z  Z   t

C
Fick’s Second Law
General solutions of the diffusion differential
Z
equation for variety of initial and boundary
J in
conditions are compromised of series of error
functions or related integrals, or are in the dJ
J out
form of trigonometric series dZ

Z
Chapter 5 - 17
Non-steady State Diffusion
• Copper diffuses into a bar of aluminum.
Surface conc.,
Cs of Cu atoms bar
pre-existing conc., Co of copper atoms Fig. 5.5,
Callister &
Rethwisch 9e.

B.C. at t = 0, C = Co for
0x∞
at t > 0, C = CS for x = 0
(constant surface conc.)
C = Co for x = ∞

Concentration
Profile

Will Vary Time 1

Over Time

Position Adapted from Dr. Simge Cinar’s Lecture

Notes, METE230, METU, Ankara,Turkey Chapter 5 - 18
Non-steady State Diffusion
• Copper diffuses into a bar of aluminum.
Surface conc.,
Cs of Cu atoms bar
pre-existing conc., Co of copper atoms Fig. 5.5,
Callister &
Rethwisch 9e.

B.C. at t = 0, C = Co for
0x∞
at t > 0, C = CS for x = 0
(constant surface conc.)
C = Co for x = ∞

Concentration
Profile

Will Vary Time 2

Over Time

Position Adapted from Dr. Simge Cinar’s Lecture

Notes, METE230, METU, Ankara,Turkey Chapter 5 - 19
Non-steady State Diffusion
• Copper diffuses into a bar of aluminum.
Surface conc.,
Cs of Cu atoms bar
pre-existing conc., Co of copper atoms Fig. 5.5,
Callister &
Rethwisch 9e.

B.C. at t = 0, C = Co for
0x∞
at t > 0, C = CS for x = 0
(constant surface conc.)
C = Co for x = ∞

Concentration
Profile

Will Vary Time 4 >> Time 0

Over Time

Position Adapted from Dr. Simge Cinar’s Lecture

Notes, METE230, METU, Ankara,Turkey Chapter 5 - 20
Kirkendall Effect

Cu Ni
DNi>DCu
Cu Ni Cu Ni
JNi
JCu Ni
Cu

Jvacnet is through Nickel site

Marker at the diffusion interface move slightly in the opposite

direction to the most rapidly moving species ⇒ vacancies can
move!

Observed in vacancy-assisted substitutional diffusion.

Chapter 5 - 21
Adapted from Prof. Dr. Sakir Bor’s Lecture Notes, METE403, METU, Ankara,Turkey
Diffusion Coefficient
 = jump frequency (1) (2)
=  of times an atom jumps to a neighboring position / second
p = probability that any jump of an atom on plane 1 will carry it to plane 2
= fraction of jumps going from plane 1 to plane 2
n1, n2 = Area concentration =  of atoms/cm2 on planes 1 and 2.
An individual atom will jump from plane 1 to plane 2 = p times per second.
No. atoms/cm2 jumping 1 to 2 in unit time = J1-2 = n1 (p)
No. atoms/cm2 jumping 2 to 1 in unit time = J2-1 = n2 (p) 

Net No. atoms/cm2 jumping 1 to 2 = Jnet (atom/sec-cm2) = (n1 - n2) (p)

𝜕𝐶
𝐶2 = 𝐶1 + 𝑎
𝜕𝑧
2 C
n 2 - n1 = 
Z
C Comparing this equation with
J = - 2  p   
Z Fick's first law, D =2 p 
Chapter 5 - 22
Diffusion Coefficient and Temperature
Qd
D = Do exp −
RT

D = diffusion coefficient [m2/s]

Do = pre-exponential [m2/s]
Qd = activation energy [J/mol or eV/atom]
R = gas constant [8.314 J/mol-K]
T = absolute temperature [K]

Chapter 5 - 23
 Diffusion and Temperature
D has exponential dependence on T
1500

1000

600

300
T(°C)
10-8

D (m2/s) Dinterstitial >> Dsubstitutional

C in α-Fe Al in Al
10-14 C in γ-Fe Fe in α-Fe
Fe in γ-Fe

10-20
0.5 1.0 1.5 1000 K/T

Adapted from Fig. 5.7, Callister & Rethwisch 9e.

(Data for Fig. 5.7 taken from E.A. Brandes and G.B. Brook (Ed.) Smithells Metals
Reference Book, 7th ed., Butterworth-Heinemann, Oxford, 1992.)

Chapter 5 - 24
Example: At 300oC the diffusion coefficient and
activation energy for Cu in Si are
D(300oC) = 7.8 x 10-11 m2/s
Qd = 41.5 kJ/mol
What is the diffusion coefficient at 350oC?

D transform ln D
data

Temp = T 1/T

Chapter 5 - 25
 Example (cont.)

T1 = 273 + 300 = 573K

T2 = 273 + 350 = 623 K

D2 = 15.7 x 10-11 m2/s

Chapter 5 - 26
Interface Diffusion
-6
2000 1750 1500 C
10

-8 Surface
10
Dsurface > DGB > Dlattice
-10
10
Qsurface < QGB < Qlattice D
Grain boundary

-12
10
Qlattice  2 QGB  2 Qdislocation Lattice
-14
10

-16
10
3 4 5 6 7
4 -1
1 / T x 10 (K )

Chapter 5 - 27
Grain-boundary diffusion
makes a significant
contribution to the total
diffusion only when the DLAL
grain size is quite small so
that DGBAGB
(fine grained)
JGBAGB >JLAL D
or DGB
where A’s are cross DxA
DGBAGB
sectional areas of the grain DLattice (coarse grained)
boundaries and the lattice,
i.e., when
High T Low T
DGB > (AL/AGB) Dlattice . Lattice GB
diffusion diffusion
dominant dominant

Grain-boundary diffusion
1 / Tc 1 / Tc
may become dominant
over lattice diffusion only at
lower temperatures.
Chapter 5 - 28
 Summary
Diffusion FASTER for... Diffusion SLOWER for...

• open crystal structures • close-packed structures

• materials w/secondary • materials w/covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• lower density materials • higher density materials

Chapter 5 - 29
An FCC iron–carbon alloy initially containing 0.55 wt% C is exposed to an oxygen-rich and virtually carbon-free atmosphere
at 1325 K (1052°C). Under these circumstances the carbon diffuses from the alloy and reacts at the surface with the oxygen in
the atmosphere—that is, the carbon concentration at the surface position is maintained essentially at 0 wt% C. (This process of
carbon depletion is termed decarburization.) At what position will the carbon concentration be 0.25 wt% after a 10-h
treatment? The value of D at 1325 K is 3.3 ×10–11m2/s.

Chapter 5 -
A sheet of BCC iron 2-mm thick was exposed to a carburizing gas atmosphere on one side and a decarburizing atmosphere
on the other side at 675°C. After reaching steady state, the iron was quickly cooled to room temperature. The carbon
concentrations at the two surfaces of the sheet were determined to be 0.015 and 0.0068 wt%, respectively. Compute the
diffusion coefficient if the diffusion flux is 7.36 ×10–9 kg/m2s. (Hint: Use Equation 4.9 to convert the concentrations from
weight percent to kilograms of carbon per cubic meter of iron: the densities of carbon and iron are 2.25 g/cm3and 7.87
g/cm3)

Chapter 5 -
Chapter 5 -